Heat shrinkable barrier bags with anti block additives

ABSTRACT

A multiple layer polymeric film having five layers and wherein an antiblock additive and an slip additive may optionally and independently be present in layers  1, 2, 4  and  5  and wherein said antiblock additive may be a blend of two or more antiblock additives and wherein both of said slip additive and said antiblock additives are present at about 0.1%-10%, based on the total weight of the layer.

[0001] This application is a continuation-in-part of U.S. patentapplication Ser. No. 09/573,596, filed May 18, 2000; which is acontinuation of U.S. patent application Ser. No. 09/105,623, filed Jun.26, 1998, now U.S. Pat. No. 6,074,715; which is a continuation-in-partof U.S. patent application Ser. No. 08/886,881, filed Jul. 2, 1997(abandoned); which is a continuation of U.S. patent application Ser. No.08/653,520, filed May 15, 1995 (abandoned); which is a continuation ofU.S. patent application Ser. No. 08/082,226, filed Jun. 24, 1993(abandoned).

BACKGROUND OF THE INVENTION

[0002] The present invention relates to a five layer heat shrinkablebarrier bag wherein an antiblock additive may independently be presentin layers 1, 2, 4 and 5. These heat shrinkable film structures areuseful in packaging meats.

[0003] Polymeric materials have many applications in packagingstructures. They are used as films, sheets, lidstock, pouches, tubes andbags. These polymeric materials may be employed as a single layer or oneor more layers in a structure. Unfortunately, there are countlesspolymeric materials available. Furthermore, resin suppliers frequentlyhave a tendency to claim many more applications for a product than theproduct is actually suitable for. In addition, in view of thespecialized applications and processing problems that are encountereddespite the suppliers claims, one skilled in the art can not tellwhether a particular resin will be suitable for an application unlesstested. However, for various reasons there are frequently drawbacks tothe use of many of these polymeric materials. For example, ethylenevinyl alcohol is an excellent oxygen barrier material for use inpackaging food products. However, this polymeric material can beaffected by moisture that is present in the atmosphere or the packagedproduct. As a result, it is frequently found that some polymericmaterials are better for certain applications than others.

[0004] One area where there is a need for suitable resins in filmapplications is in the area of heat shrinkable films. Heat shrinkablepolymeric films are commonly used in packaging meats, particularlyprimal meat cuts and other large pieces of meat. While this descriptionwill detail the usage of films for packaging meat and meat by-products,it will be understood that these films are also suitable for packaging amyriad of other products, both including food products and non-foodproducts.

[0005] Some of the films embodying the present invention are intended tobe used by meat packers in the form of heat shrinkable bags with oneopened end, which bags are closed and sealed after insertion of themeat. After the product is inserted, air is usually evacuated from thepackage and the open end of the bag is closed. Suitable methods ofclosing the bag include heat sealing, metal clips, adhesives etc. Heatis applied to the bag once sealing is completed to initiate shrinkage ofthe bag about the meat.

[0006] In subsequent processing of the meat, the bag may be opened andthe meat removed for further cutting of the meat into user cuts, forexample, for retail cuts or for institutional use.

[0007] Suitable shrink bags must satisfy a number of criteria. Many bagusers seek a bag that is capable of surviving the physical process offilling, evacuating, sealing and heat shrinking. For example, during theshrinking process great stress can be placed on the film by the sharpedges of bone in the meat. The bag must also have sufficient strength tosurvive the material handling involved in moving the large cuts of meat,which may weigh fifty pounds or more, along the distribution system.

[0008] Because many food products including meat deteriorate in thepresence of oxygen and/or water, it is desirable that the bags have abarrier to prevent the infusion of deleterious gases and/or the loss oraddition of moisture.

[0009] Conventional packaging for many products has frequently been madeof multiple layer films having at least three layers. These multiplelayer films are usually provided with at least one core layer of eitheran oxygen barrier material such as a vinylidene chloride copolymer,ethylene vinyl alcohol, a nylon or a metal foil preferably aluminum.Heat shrinkable meat bags, for example, have generally used vinylidenechloride copolymers. The copolymer of the vinylidene chloride may, forexample, be a copolymer with vinyl chloride or methyl acrylate.Collapsible dispensing tubes have generally used one or more foillayers. The foil layers in addition to supplying an oxygen barrier alsoprovide the dispensing tube with “deadfold”, i.e., the property of acollapsible dispensing tube when squeezed to remain in the squeezedposition without bouncing back.

[0010] Outer layers of films used in packaging food products can be anysuitable polymeric material such as linear low density polyethylene, lowdensity polyethylene, ionomers including sodium and zinc ionomers, suchas Surlyn®. In conventional shrink bags, the outer layers are generallylinear low density polyethylene or blends thereof. Suitable outer layersfor meat bags are taught by U.S. Pat. No. 4,457,960 to Newsome, thedisclosures of which are incorporated herein by reference.

[0011] U.S. Pat. No. 4,894,107 to Tse et al. commonly assigned toAmerican National Can discloses novel films and processes for makingthem. The films are characterized by having first and second layerswhose compositions have a significant fraction of ethylene vinyl acetate(EVA). A third layer of vinylidene chloride copolymer (VDC-CP) isdisposed between the first and second layers. The composition of atleast one of the first and second layers is a blend of 10% by weight to90% by weight linear low density polyethylene (LLDPE) and 90% to 10%EVA. These polymeric films are useful as heat shrinkable polymericfilms. The film may be unoriented or oriented. Oriented films may beoptionally cross-linked.

[0012] While conventional films have been suitable for manyapplications, it has been found that there is a need for films that arestronger and more easily processed than conventional films. In meatbags, there is a need for films and bags that have superior toughnessand sealability and the ability to undergo cross-linking without unduedeterioration. Thus, it is an object of the present invention to provideimproved structures, including single and multi-layer films, sheets,lidstock, pouches, tubes and bags. In particular, structures for use inshrink bags wherein the shrink bags are capable of withstandingproduction stresses and the shrink process.

SUMMARY OF THE INVENTION

[0013] The structures of the present invention may be single ormultilayer films, sheets, lidstock, pouches, containers, tubes and bagswhere at least one layer contains a polymer, usually a copolymer, formedby a polymerization reaction in the presence of a single site catalystsuch as a metallocene. Examples of such a polymer are ethylene andpropylene polymers and copolymers thereof. One preferred copolymer is acopolymer of ethylene and an alpha olefin where such alpha olefin has acarbon chain length of from C₃-C₂₀. The structures of the presentinvention may also include blends of polymers and copolymers formed by apolymerization reaction with a single site catalyst or blends of apolymer and copolymer formed by a polymerization reaction with a singlesite catalyst and another polymeric material. Examples of suitablepolymers for blending include: high and medium density polyethylene(HDPE, MDPE), linear low density polyethylene (LLDPE), low densitypolyethylene (LDPE), ethylene vinyl acetate (EVA), ultra low densitypolyethylene (ULDPE or very low density polyethylene VLDPE), andionomers such as Surlyn®. Polymers made from single site catalyst,preferably metallocene catalysts, provide increased strength,particularly seal, burst, impact and puncture as well as improved opticsand faster bag making/sealing speeds.

[0014] The present invention may also be a multilayer structure of atleast three layers wherein the core layer is a barrier layer. In oneembodiment of the present invention, there may be a first outer layer ofan ethylene or propylene polymer or copolymer formed by a polymerizationreaction in the presence of a single site catalyst, a barrier layer anda second outer layer of a polymeric material. The second outer layer maybe an ethylene or propylene polymer or copolymer formed by apolymerization reaction in the presence of a single site catalyst or alayer of another polymeric material such as high density polyethylene,medium density polyethylene, linear low density polyethylene, ultra lowdensity polyethylene, low density polyethylene, ethylene vinyl acetate,an ionomer or blends thereof. The first outer layer may also be a blendof the ethylene copolymer with another suitable polymeric material suchas described above. A preferred polymer formed by a single site catalystis a copolymer of ethylene and an alpha olefin such as 1-octene.Additional layers such as adhesive layers or other polymeric layers maybe interposed in the structure between one or both of the outer layersor on top of one or both of the outer layers. The structure of thepresent invention may be rendered oriented either uniaxially orbiaxially and cross-linked by any suitable means, such as for exampleirradiation or chemical cross-linking.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015]FIG. 1 is a side view of a three layer structure of the presentinvention.

[0016]FIG. 2 is a side view of a five layer film of the presentinvention.

[0017] FIGS. 3-6 are examples of the structure of metallocene catalystswhich could be used in the polymerization of the polymer used in thestructures of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The structures of the present invention include films, sheets,lidstock, pouches, containers, tubes and bags. These structures may be asingle layer or multi-layer structure. The structures are comprised ofpolymers that have been polymerized in the presence of a single sitecatalyst, such as a metallocene. A metallocene is a complexorganometallic molecule typically containing zirconium or titanium, witha pair of cyclic alkyl molecules. More specifically, metallocenecatalysts are usually compounds with two cyclopentadiene rings fixed tothe metal. These catalysts are frequently used with aluminoxanes as acocatalyst or an activator, one suitable aluminozane is amethaluminoxane (MAO). Besides, titanium and zirconium, hafnium may alsobe used as the metal to which the cyclopentadiene is bonded. Alternativemetallocenes may include Group IVA, VA and VIA transition metals withtwo cyclopentadiene rings. Also mono-cyclopentadiene rings or silylamides may alternatively be in the metallocene instead of twocyclopentadienes. Other metals to which the cyclopentadiene may beattached may include the metals in the lanthanide series. FIGS. 3, 4, 5and 6 show representative metallocenes that are suitable single sitecatalysts.

[0019] While the reaction mechanism is not completely understood, it isbelieved that the metallocene, single site catalyst confines thecopolymerization reaction to a single site over the polymer thuscontrolling comonomer placement and side chain length and branching. Thecopolymers formed from metallocene single site catalysts are highlystereo regular products with narrow molecular weight distribution. Themetallocenes can be used to polymerize ethylene, propylene, ethylenicand acetylenic monomers, dienes and carbon monoxide. Comonomers withethylene and propylene include styrene, substituted styrene and1,4-hexadiene. The metallocene single site catalysts are capable ofproducing isotactic polymers and syndiotactic polymers, i.e., polymersin which the crystalline branches alternate regularly on both sides ofthe back bone of the polymer. There are two general types of single sitecatalyst reactions. The first are stereoselective catalysts reactionswhich have been developed by Exxon and Dow and which are used to makeExxon's Exact resins and Dow's constrained geometry catalyst technology(CGCT) resins. See FIGS. 3 and 4. The second type of reactions arestereoselective catalysts developed by Hoechst and Fina for stereospecific polymerization particularly of polypropylene and other olefmssuch as 1-butene and 4-methyl-1-pentene. See, e.g., FIGS. 5 and 6.

[0020] The ethylene alpha olefins polymerized by a single site catalystcan have low crystallinity and a density that ranges from 0.854 to 0.97gm/cc. Although this density range is similar to conventional ethylenepolymers, i.e., LDPE, LLDPE and ULDPE, the polymers in the structures ofthe present invention have a narrow molecular weight distribution andhomogeneous branching. The molecular weight distribution of thepreferred polymers may be represented by the formula

MWD=M _(w) /M _(n)=<2.5

[0021] In addition, the melt processability of these polymers (I₁₀/I₂)has a range of about 5.5 to about 12 while conventional homogenouspolymers are generally less than 6.5 at an MWD of 2. The melt tension ofthese polymers is in the range of about 1.5 to 3.5 grams.

[0022] The MWD of these polymers may be determined using a Water's 150GPC at 140° C. with linear columns (103₆ A-10₆ A₀) from Polymer Labs anda differential refractometer detector. Comparison of the MWD of a 1MI,0.920 density CGCT polymer with that of 1MI, 0.920 density conventionalLLDPE illustrates the very narrow MWD of the CGCT polymers which usuallyhave a M_(W)/M_(N) of approximately 2 compared to 3 or greater forLLDPE.

[0023] A preferred ethylene copolymer is a copolymer of ethylene and aC₃ to C₂₀ alpha olefin. A preferred copolymer is a low modulus ethyleneoctene copolymer sold by Dow. This copolymer is formed by Dow'sconstrained-geometry catalyst technology which uses a single sitecatalyst such as cyclo-pentadienyl titanium complexes. As bestunderstood, Dow's constrained geometry catalysts are based on group IVtransition metals that are covalently bonded to a monocyclopentadienylgroup bridged with a heteroatom. The bond angle between themonocyclopentadienyl group, the titanium center and the heteroatom isless than 115°. When the alpha olefin is present in the copolymer in therange of about 10 to 20% by weight these copolymers are referred to asplastomers. When the percent alpha olefin is greater than 20% thesecopolymers are called elastomers. The preferred ethylene octenecopolymer has the octene comonomer present in an amount less than 25%.Examples of Dow ethylene octene copolymers have the following physicalproperties. MOLECULAR MELT DENSITY WEIGHT MELT FLOW MELT g/ccDISTRIBUTION INDEX RATIO STRENGTH 0.920 1.97 1.0 9.5 1.89 0.910 1.90 1.07.9 1.68 0.902 2.10 1.0 7.6 1.68

[0024] Molecular weight distribution is defined as the ratio of weightaverage molecular weight to number average molecular weight. The lowerthe figure, the narrower the molecular weight distribution. Melt flowratio is defined as the ratio of melt index, as tested with a 10-kg loadto the melt index with a 2.168-kg load. The higher the ratio, the moreprocessable the material. Melt strength is defined as melt tensionmeasured in grams. The higher the number the greater the melt strength.Other suitable resins are the Exact resins sold by Exxon, these resinshave the following characteristics: TYPICAL PROPERTIES OF EXACT MEDICALGRADE POLYETHYLENES VALUE BY GRADE PROPERTY 4028 4022 4021 4023 40244027 Melt index (D1238)* 10 6 22 35 3.8 4 Density, g./cc. (D-1505) 0.8800.890 0.885 0.882 0.885 0.895 Hardness (D-2240) Shore A 78 84 84 80 8389 Shore D 29 35 36 27 35 39 Tensile strength at 2220 1700 3260 620 28402200 break, p.s.i. (D-638) Tensileelongation >800 >800 >800 >800 >800 >800 at break, % (D-638) Tensileimpact, 145 130 350 280 300 340 ft.-lb./sq. in. (D-1822) Flexuralmodulus, 5040 4930 3980 3100 4180 7230 p.s.i. (D-790) Vicat softening138 168 158 138 158 181 point ° F. (D-1525)

[0025] The structure of the present invention is comprised of anethylene, propylene, or styrene polymer or copolymer formed by apolymerization reaction in the presence of a single site catalystpreferably a metallocene. Ethylene may be copolymerized with anysuitable monomer such as C₃-C₂₀ alpha olefin including propylenebutene-1, 4-methy-1-pentene, 1-hexene and 1-octene. A preferredcomonomer is 1-octene. The preferred ethylene alpha olefin copolymer ofthe present invention has a density in the range of 0.880 gm/cc to about0.920 gm/cc, a more preferred range of 0.890 gm/cc to about 0.915 gm/ccand a most preferred range of about 0.900 gm/cc to about 0.912 gm/cc.

[0026]FIG. 1 shows a cross section of a three layer coextrudedstructure. Layer 14 is the core layer which may be a barrier layer thatminimizes the transmission of oxygen through the structure. Preferredbarrier materials are polyvinylidene chloride copolymers such ascopolymers of vinylidene chloride and vinyl chloride or an alkylacrylate such as methyl acrylate. Other preferred barrier materialsinclude, ethylene vinyl alcohol, nylon or a metal foil such as aluminum.Layer 14 may also be a copolymer of ethylene and styrene formed using asingle site catalyst in the polymerization reaction. In addition, layer14 may also be a polystyrene formed by a polymerization reaction in thepresence of a single site catalyst. One such polystyrene is thecrystalline syndiotactic polystyrene sold by Idemitsu Petro-ChemicalCo., Tokyo, Japan.

[0027] On opposite sides of the core layer 14 of FIG. 1 are layers 12and 16. At least one of these layers 12 is a polymer formed by apolymerization reaction in the presence of a single site catalyst. Theremaining layer 16 may be any suitable polymeric material or blends ofmaterial such as a polyester, co-polyester, polyamide, polycarbonate,polypropylene, propylene-ethylene copolymer, ethylene-propylenecopolymer, combinations of polypropylene and ethylene vinyl acetatecopolymer, ultra low density polyethylene, low density polyethylene,medium density polyethylene, high density polyethylene, linear lowdensity polyethylene copolymers, linear medium density polyethylenecopolymer, linear high density polyethylene copolymer, ionomer, ethyleneacrylic acid copolymer, ethylene ethyl acrylate copolymer, ethylenemethyl acrylate copolymer, or ethylene methacrylic acid copolymer.

[0028] In an alternate embodiment, the layer 12 may be a blend of apolymer formed by a polymerization reaction in the presence of a singlesite catalyst and a suitable polymeric material such as is identified inconnection with the description of layer 16 above.

[0029] As seen in FIG. 2, the structure may also include embodimentswhich have a fourth layer 28 over the first layer 22 and a fifthpolymeric layer 30 over the third layer 26. The composition of thefourth layer 28 may be selected from the same group of materials fromwhich the composition of the first layer 12 or third layer 16 isselected, and the fifth layer 30 may also be the same composition as thefirst layer 22 or the third layer 26.

[0030] In an alternate embodiment of FIG. 2, the five layer structuremay have a first layer 28 similar in composition to layer 12 of FIG. 1,i.e., the film may have a first layer of a polymer formed by thepolymerization reaction with a single site catalyst or blends thereofwith another suitable polymeric material. One or both of the second 22and fourth 26 layers may be an adhesive layer.

[0031] The composition of adhesive layers 22 and 26 is selected for itscapability to bond the core or barrier layer 24 to the surface layers 28and 30. A variety of the well known extrudable adhesive polymers adherewell to the core or barrier layer 24. Thus, if for example layer 30 is apolypropylene, an adhesive polymer based on polypropylene is desirablyselected for layer 26. Examples of such adhesives are the extrudablepolymers available under the trade designations Admer QF-500, QF550, ofQF-551 from Mitsui Petrochemical Company, or Exxon 5610A2.

[0032] If the composition of layer 23 or 30 is an ethylene based polymeror copolymer, an adhesive polymer based on ethylene is preferablyselected for layer 22, including ethylene homopolymer and copolymers.Such a preferred adhesive composition is an ethylene vinyl acetatecopolymer (EVA) containing up to 25% to 30% by weight vinyl acetate.Other ethylene based homopolymer and copolymers, modified to enhanceadhesion properties are well known under the trade names of, forexample, Bynel and Plexar. Typical base polymers for these extrudableadhesives are the polyethylene LLDPE and the ethylene vinyl acetatecopolymers. Such adhesive polymers, including the polypropylene-basedpolymers, are typically modified with carboxyl groups such as anhydride.Also acceptable as adhesives are ethylene methyl acrylate copolymers(EMA).

[0033] Additional layers may also be present in the structures of thepresent invention. For example, the present invention contemplates 4, 6,7, 8, and higher numbers of layers in the film of the present inventionand different combinations of layer structures may also be present. Forexample, there may be more than one barrier layer, i.e., two layers ofpolyvinylidene chloride copolymers, two layers of foil or two layers ofethylene vinyl alcohol (EVOH) or nylon. Alternatively, this may be alayer of EVOH and a layer of a polyvinylidene chloride copolymer or apolyamide or a polystyrene and other combinations of the core materials.The additional layers of the present invention also encompass more thanone polymer formed by the polymerization reaction in the presence of asingle site catalyst. The polymers may be in a layer alone or in theform of a blend. Suitable polymers for blending with an ethylene polymerformed in a polymerization reaction with a single site catalyst includeother ethylene polymers formed in a polymerization reaction with asingle site catalyst, low density polyethylene (LDPE), linear lowdensity polyethylene (LLDPE), ultra low density polyethylene (ULDPE),EVA, ionomers, ethylene copolymers, ethylene methyl acrylate (EMA),ethylene acrylic acid (EAA), ethyl methyl acrylic acid (EMAA),polypropylene (PP), ethylene normal butyl acrylate (ENBA), ethylenepropylene copolymers (PPE). Suitable polymers for blending with apropylene polymers formed in a polymerization reaction with a singlesite catalyst include ethylene propylene copolymers.

[0034] Preferred blends using EVA's are those having lower vinyl acetate(VA) content as they tend to yield EVA layers having better hotstrength. EVA's having higher VA content tend to yield EVA layers havingincreased adhesion to for example, the vinylidene chloride copolymerlayer. EVA's having virtually any amount of VA will have better adhesionto the vinylidene chloride copolymer layer than an ethylene homopolymer.However, good interlayer adhesion is considered desirable in theinvention, and thus, steps are usually taken to enhance adhesion whereno unacceptable negative effect is encountered. Thus, higher VAcontents, in the range of 6% to 12% vinyl acetate are preferred, a meltindex of less than 1 is also preferred. While blend amounts are shownherein in weight percent, VA contents are mole percent. Especiallypreferred EVA's have VA content of 7% to 9% and melt index of 0.2 to0.8. Blends of EVA's to make up the EVA component of layers 16 and 18are acceptable.

[0035] Preferred structures of the invention are represented by amultiple layer polymeric film having five layers wherein one of the fivelayers is composed of vinylidene chloride methyl acrylate.

[0036] In a preferred embodiment of the invention, the multiple layerpolymer film comprises a first layer, the composition of said firstlayer comprising a blend of an ethylene vinyl acetate copolymer; linearlow density polyethylene; a second ethylene vinyl acetate copolymer; andslip additive; a second layer, the composition of said second layercomprising ethylene vinyl acetate and wherein each first and secondlayer having two surfaces; a third layer, the composition of said thirdlayer comprising vinylidene chloride methyl acrylate and wherein saidthird layer is disposed between said first and second layer; a fourthlayer, the composition of said fourth layer being the same as said firstlayer wherein said fourth layer is adhered to said first layer on thesurface opposite said third layer; and a fifth layer, the composition ofsaid fifth layer comprising a blend of linear low density polyethyleneand low density polyethylene wherein said fifth layer is adhered to saidsecond layer on the surface opposite said third layer.

[0037] In a further preferred embodiment of the invention, the firstlayer of the multiple layer polymeric film is a blend of 80% by weightof ethylene vinyl acetate copolymer; 10% by weight of linear low densitypolyethylene; 9.65% by weight of a second ethylene vinyl acetatecopolymer; and 0.35% by weight of slip.

[0038] The second layer of the multiple, five layer polymeric film is100% by weight of ethylene vinyl acetate copolymer.

[0039] The third layer of the multiple polymeric film is 98.1% by weightof vinylidene chloride methyl acrylate and 1.9% by weight of additives.

[0040] The fourth layer of the multiple layer polymeric film is a blendof 80% by weight of ethylene vinyl acetate copolymer; 10% by weight oflinear low density polyethylene; 9.65% by weight of a second ethylenevinyl acetate copolymer; and 0.35% by weight of slip additive.

[0041] The fifth layer of the multiple, five layer polymeric film is ablend of 90% by weight of linear low density polyethylene and 10% byweight of low density polyethylene.

[0042] A preferred embodiment of the present invention, the multiplelayer polymer film comprises a first layer, the composition of saidfirst layer comprising a blend of an ethylene vinyl acetate copolymer;linear low density polyethylene; a second ethylene vinyl acetatecopolymer and slip additive; a second layer, the composition of saidsecond layer comprising ethylene vinyl acetate copolymer and whereineach first and second layer having two surfaces; a third layer, thecomposition of said third layer comprising vinylidene chloride methylacrylate copolymer and wherein said third layer is disposed between saidfirst and second layer; a fourth layer, the composition of said fourthlayer being the same as said first layer wherein said fourth layer isadhered to said first layer on the surface opposite said third layer;and a fifth layer, the composition of said fifth layer comprising ablend of linear low density polyethylene and low density polyethylenewherein said fifth layer is adhered to said second layer on the surfaceopposite said third layer and wherein an antiblock additive and an slipadditive may optionally and independently be present in layers 1, 2, 4and 5 and wherein said antiblock additive may be a blend of two or moreantiblock additives and wherein both of said slip additive and saidantiblock additives are present at about 0.1%-10%, based on the totalweight of the layer.

[0043] A still further preferred embodiment of the present invention,the multiple layer polymer film comprises a first layer, the compositionof said first layer comprising a blend of 80% by weight ethylene vinylacetate copolymer, 10% by weight of linear low density polyethylene;9.65% by weight of a second ethylene vinyl acetate copolymer; and 0.35%by weight of slip additive. a second layer, the composition of saidsecond layer comprising 100% ethylene vinyl acetate copolymer andwherein each first and second layer having two surfaces; a third layer,the composition of said third layer comprising 100% vinylidene chloridemethyl acrylate copolymer (96.5% by weight of vinylidene chloride methylacrylate and 3.5% by weight of processing aids) and wherein said thirdlayer is disposed between said first and second layer; a fourth layer,the composition of said fourth layer being the same as said first layerwherein said fourth layer is adhered to said first layer on the surfaceopposite said third layer; and wherein said fourth layer furthercomprises an antiblock additive wherein said antiblock additive may be ablend of two or more antiblock additives and wherein both of said slipadditive and said antiblock additives are present at about 0.1% -10%,based on the total weight of the layer; and a fifth layer, thecomposition of said fifth layer comprising a blend of 90% linear lowdensity polyethylene and 10% by weight of low density polyethylenewherein said fifth layer is adhered to said second layer on the surfaceopposite said third layer.

[0044] In the preferred embodiments of the present invention theanti-block additive is selected from Ampacet 7012124 or Ampacet 10579which are products of Ampacet Corporation, Mount Vernon, N.Y. Theanti-block additives may be present in the film structure as a singleanti-block additive or as a blend of anti-block additives.

[0045] In the preferred embodiments of the present invention, thecomposition of said fourth layer comprises 77.60% by weight of ethylenevinyl acetate copolymer; 9.7% by weight of linear low densitypolyethylene, 9.36% by weight of a second ethylene vinyl acetatecopolymer, 0.34% by weight of slip additive, 1.0% by weight of anantiblock additive and 2% by weight of processing aids. Ethylene vinylacetate resins suitable for the practice of this invention areexemplified by ESCORENE® (LD-318) and ESCORENE® (LD-712) from ExxonChemical.

[0046] EXCORENE® LD-318 is a 9.0% vinyl acetate copolymer film resin.This resin has the following properties: Resin Properties ASTM MethodUnits (SI) Typical Value² Melt Index Exxon Method g/10 min. 2.0 DensityExxon Method g/cm³ 0.930 Vinyl Acetate Exxon Method % by wt. 9.0 MeltingPoint Exxon Method ° F.(° C.) 210 (99)

[0047] ESCORENE® LD-712 is a 10.0% vinyl acetate copolymer film resin.This resin has the following properties: Resin Properties ASTM MethodUnits (SI) Typical Value³ Melt Index Exxon Method g/10 min. 0.35 DensityExxon Method g/cm³ 0.931 Vinyl Acetate Exxon Method % by wt. 10 MeltingPoint Exxon Method ° F.(° C.) 207 (97)

[0048] ESCORENE® LD-318 is suitable for the 9.65% of EVA of layers oneand four and ESCORENE® LD-712 is suitable for the remaining ethylenevinyl acetate of layers one, two and four.

[0049] Linear low density polyethylene resin suitable for the practiceof this invention is exemplified by DOWLEX® 2267A and DOWLEX® 2247A fromDow Chemical Company.

[0050] DOWLEX® 2267A has the following properties: Physical PropertiesASTM Method Values⁽¹⁾:English (SI) Resin Properties Melt Index, gm/10min D 1238 0.85 Density, gm/cc D 792 0.917 Vicat Softening Point, ° F. D1525 208 (98) (° C.)

[0051] DOWLEX® 2247A has the following properties: Physical PropertiesASTM Method Values⁽¹⁾:English (SI) Resin Properties Melt Index, gm/10min D 1238 2.3 Density, gm/cc D 792 0.917 Vicat Softening Point, ° F. D1525 210 (99) (° C.)

[0052] Alternatively, Exxon's EXCEED® 363C32 linear low densitypolyethylene resin may also be used in the structure of the presentinvention. EXCEED® 363C32 has the following properties: ResinProperties¹ Units (SI) Typical Value³ Melt Index g/10 min. 2.5 Densityg/cm³ 0.917 Melting Point ° F. (° C.) 239 (115)

[0053] In the preferred embodiment of the present invention, the lowdensity polyethylene resin suitable for the practice of this inventionis exemplified by PETROTHENE® NA204-000 from Equistar Chemicals, L. P.PETROTHENE® has the following properties: Value Units ASTM Test MethodDensity 0.918 g/cm³ D1505 Melt Index 7.0 g/10 min. D 1238 Melt Point106.5 ° C.

[0054] The polyvinylidene chloride methyl acrylate copolymer polymer ofthe present invention contains between 3 mole percent and 20 molepercent of methyl acrylate. These more preferred copolymers have 6 to 12mole percent methyl acrylate. Additives typically used with vinylidenechloride copolymers may be used in conventional amounts which would beknown to one skilled in the art. Said additives are exemplified byethylene vinyl acetate, dibutylsebacate, magnesium oxide, stearamide,and epoxidized soy bean oil.

[0055] Slip is a coefficient of friction additive which is selected fromerucamide and other fatty acid amides.

[0056] The structure of the present invention may be formed by anyconventional process. Such processes include extrusion, coextrusion,extrusion coating, extrusion lamination, adhesive lamination and thelike, and combinations of processes. The specific process or processesfor making a given film which is neither oriented nor cross-linked canbe selected with average skill, once the desired structure andcompositions have been determined.

[0057] When the structure of the present invention is a film, the filmmay also be oriented either uniaxially or biaxially. Orientation canalso be done by any conventional process for forming multiple layerfilms. A preferred process includes the steps of coextrusion of thelayers to be oriented, followed by orientation in one of theconventional processes such as blown tubular orientation or stretchorientation in the form of a continuous sheet; both being molecularorientation processes. The double bubble technique disclosure in Pahlke,U.S. Pat. No. 3,456,044 is suitable for use in producing the film ofthis invention. The films may also be formed by a tubular water quenchprocess. In this process the film may be extruded downwardly as a tubeformed by an annular die, and carried into a water quench tank,generally with a cascade of water on the outside surface providinginitial cooling. The flattened tape is withdrawn from the quench bath,is reheated (normally in a second water bath) to its orientationtemperature, is stretched in the machine direction between two sets ofrolls that are so rotated as to establish a linear rate differentialtherebetween, and is simultaneously oriented in the transverse, orcross-machine, direction as an inflated bubble trapped between the nipsof the rolls. In accordance with conventional practice, the film willusually be cooled by air in the orientation zone.

[0058] The film of the present invention may also be oriented and/orcross-linked. The first step is the formation of a multiple layer film.The formation of the multiple layer film, is usually most easilyaccomplished by coextrusion of the desired layers. Other formationprocesses are acceptable so long as the resulting oriented film at theconclusion of fabrication processing is a unitary structure.

[0059] The second step is orienting the multiple layer film. One methodfor accomplishing orientation is by heating the film to a temperatureappropriate to molecular orientation and molecularly orienting it. Thefilm may then be optionally heat set by holding it at an elevatedtemperature while its dimensions are maintained. The orientation step ispreferentially carried out in line with the first step, which is thefilm formation step of the process.

[0060] The third step is subjecting the formed and oriented multiplelayer film, to electron beam irradiation.

[0061] The amount of electron beam irradiation is adjusted, depending onthe make-up of the specific film to be treated and the end userequirement. While virtually any amount of irradiation will induce somecross-linking, a minimum level of at least 1.0 megarads is usuallypreferred in order to achieve desired levels of enhancement of the hotstrength of the film and to expand the range of temperature at whichsatisfactory heat seals may be formed. While treatment up to about 50megarads can be tolerated, there is usually no need to use more than 10megarads, so this is a preferred upper level of treatment the mostpreferred dosage being 2 to 5 megarads.

[0062] The third step of subjecting the film to electron beamirradiation is performed only after the multiple layer film has beenformed, and after molecular orientation, in those embodiments where thefilm is molecularly oriented. It should be noted that, in theirradiation step, all of the layers in the film are exposedsimultaneously to the irradiation sources, such that irradiation of allthe layers of the film takes place simultaneously.

[0063] In one embodiment of the process, the second step of orientationmay be omitted and the unoriented multiple layer film may becross-linked by irradiation treatment to produce a cross-linked,unoriented, multiple layer film.

[0064] Multilayer heat shrinkage films of the present invention may alsocontain an optical brightner. The films which contain an opticalbrightner counteract the effects of yellowing in the oxygen barriermaterial of the multilayer heat shrinkable films.

[0065] In a still preferred embodiment of the heat shrinkable films, themultiple layer polymer film comprises a first layer, the composition ofsaid first layer comprising a blend of an ethylene vinyl acetatecopolymer; linear low density polyethylene; a second ethylene vinylacetate copolymer; and slip; a second layer, the composition of saidsecond layer comprising ethylene vinyl acetate and wherein each firstand second layer having two surfaces; a third layer, the composition ofsaid third layer comprising vinylidene chloride methyl acrylate whereina violet pigment is incorporated into the vinylidene chloride methylacrylate copolymer layer and wherein said third layer is disposedbetween said first and second layer; a fourth layer, the composition ofsaid fourth layer being the same as said first layer wherein said fourthlayer is adhered to said first layer on the surface opposite said thirdlayer; and a fifth layer, the composition of said fifth layer comprisinga blend of linear low density polyethylene and low density polyethylenewherein said fifth layer is adhered to said second layer on the surfaceopposite said third layer and wherein an antiblock additive and an slipadditive may optionally and independently be present in layers 1, 2, 4and 5 and wherein said antiblock additive may be a blend of two or moreantiblock additives and wherein both of said slip additive and saidantiblock additives are present at about 0.1%-10%, based on the totalweight of the layer..

[0066] As used herein, “violet tint” means a color within the visiblelight spectrum which is characterized by a wavelength range of fromabout 380 to about 440 nanometers.

[0067] The multilayer heat shrinkable films which contain a coloredpigment, specifically a violet pigment, are manufactured byincorporation of the violet pigment into the barrier layer of the film.In a preferred embodiment, the violet pigment is incorporated intovinylidene-chloride-methyl acrylate copolymer layer.

[0068] For ease in manufacturing the pigmented layer of film, thepigment is used dispersed in a polymeric material. These polymericconcentrates may be prepared by using any suitable method for dispersingsolid materials in polymers. Extrusion and milling are examples of suchmethods. Generally, the polymeric material which is selected for thedisbursement of the pigment is compatible with the polymeric materialwhich is selected for the film layer. Therefore, the polymeric materialwhich functions as the dispersing agent must be dispersible into thefilm layer into which it is incorporated.

[0069] For the purpose of this invention, a polymeric concentrate maycontain pigment in an amount of 300 ppm to 800 ppm, based on the totalweight of the pigment and polymeric material combined.

[0070] Pigment may be incorporated into a film by combining thepolymeric concentrate which contains the pigment with the feed materialof one or more film layers by any suitable mixing methods. The amount ofpolymeric concentrate incorporated into a given film layer will dependon many factors. These factors include but are not limited to: thenumber of layers into which the pigment will be incorporated, thepolyvinylidene chloride copolymer content of the film, and the degree ofthermal and/or radiation exposure said polyvinylidene chloride copolymeris subjected to. A film should contain sufficient pigment to provide afilm which despite exposure of the polyvinylidene chloride copolymerlayer to radiation levels from 2.0 megarad to 6.0 megarads, retains anacceptable violet tint.

[0071] In a preferred embodiment, the vinylidene chloride methylacrylate copolymer layer contains a substituted anthraquinone in anamount of 5 to 15 ppm based on the total weight of the vinylidenechloride methyl acrylate copolymer present.

[0072] A substituted anthraquinone suitable for use is1-hydroxy-4-anilino-9, 10-anthraquinone having the following structuralformula:

EXAMPLES

[0073] Multilayer films may be prepared according to the presentinvention. Biaxially stretched three layer films may be prepared by a“double bubble” process similar to that disclosed in U.S. Pat. No.3,456,044 by coextruding the following compositions through a multilayerdie, biaxially stretching the coextruded primary tube. The films mayalso be irradiated if desired.

Example 1

[0074] Layer 1 - Copolymer of ethylene and an alpha olefin such as1-Hexene or 1-Octene formed by the polymerization reaction in thepresence of a single site catalyst or metallocene (hereinafter CEO)Layer 2 - Vinylidene chloride - methyl acrylate (VDC-MA) copolymer Layer3 - Polyolefin. This film may be biaxally stretched and if necessaryirradiated. EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 Layer 1 CEO CEO CEO-EVA blendLayer 2 VDC-MA VDC-MA VDC-MA Layer 3 ULDPE-EVA blend CEO CEO-EVA blendEXAMPLE 5 EXAMPLE 6 EXAMPLE 7 LAYER 1 CEO CEO CEO-EVA blend LAYER 2Nylon Nylon Nylon LAYER 3 CEO ULDPE-EVA CEO-EVA blend EXAMPLE 8 EXAMPLE9 LAYER 1 Polyolefin Polyolefin LAYER 2 Styrene copolymer formedPropylene copolymer by the polymerization reaction formed by the with asingle site catalyst Polymerization reaction with a single site catalystLAYER 3 Polyolefin Polyolefin EXAMPLE 10 EXAMPLE 11 EXAMPLE 12 LAYER 1CEO CEO CEO-EVA Blend LAYER 2 CEO EVOH EVOH LAYER 3 CEO ULDPE-EVA BlendCEO-EVA Blend EXAMPLE 13 EXAMPLE 14 EXAMPLE 15 LAYER 1 CEO CEO CEO-EVABlend LAYER 2 Tie Tie Tie LAYER 3 PVDC Copolymer PVDC Copolymer PVDCCopoly- or EVOH or EVOH mer or EVOH LAYER 4 Tie Tie Tie LAYER 5ULDPE-EVA Blend CEO CEO-EVA Blend EXAMPLE 16 LAYER 1 EVA-ULDPE LAYER 2ULDPE or CEO LAYER 3 PVDC Copolymer or EVOH LAYER 4 EVA LAYER 5 CEO orblend of CEO and EVA

[0075] The following examples may also be prepared in accordance withthe present invention:

Example 17

[0076] Meat Film—Forming Web

[0077] Formed by TWQ Process

[0078] (Tubular Water Quench Process)

[0079] LAYER 1 Nylon

[0080] LAYER 2 Tie

[0081] LAYER 3 EVOH

[0082] LAYER 4 Tie

[0083] LAYER 5 CEH or CEO

[0084] CEH is a copolymer of ethylene and 1-Hexene formed by thepolymerization reaction in the presence of a single site catalyst or ametallocene. Other alpha olefins can be polymerized with the ethylenealso.

Examples18-20

[0085] Innerliner Films—These films can be formed either on a blown filmline or by using a tubular water quench.

[0086] LAYER 1 HDPE

[0087] LAYER 2 Blend of CEH or CEO and EVA and polybutylene

[0088] LAYER 1 HDPE

[0089] LAYER 2 CEH or CEO and polybutylene

[0090] LAYER 1 HDPE

[0091] LAYER 2 CEH or CEO

Examples 21 and 22

[0092] Meat—Non Forming Top Web film

[0093] LAYER 1 PVDC coated PET

[0094] LAYER 2 Adhesive (lamination)

[0095] LAYER 3 CEO or CEH

[0096] This film may be formed by adhesive laminating a film formed of acopolymer of ethylene and an alpha olefin with the PVDC coated PET film.

[0097] LAYER 1 PVDC coated PET

[0098] LAYER 2 LDPE—extrusion laminated

[0099] LAYER 3 LDPE/CEH or CEO coextrusion

[0100] This film can be formed by extrusion laminating a film of PVDCcoated PET or LDPE.

Example 23

[0101] Layer 1—Blend of two or more copolymers of ethylene and an alphaolefin polymerized in the presence of a single site catalyst ormetallocene such as CEO with either CEH or CEB. CEB is a copolymer ofethylene and butene-1 formed by a polymerization reaction in thepresence of a single site catalyst or a metallocene.

Example 24

[0102] Layer 1—Blend of a copolymer of ethylene and an alpha olefinformed by a polymerization reaction in the presence of a single sitecatalyst or a metallocene with Polyethylene or other polyolefin such asEVA, EMA, FAA, EMAA, ionomers, ENBA, PP or PPE.

[0103] The films of example 23 and 24 can either be single layer filmsor multi layer films where additional layers are present on layer 1.

Example 25

[0104] A four layer film was coextruded at a total caliper of 2.1, 2.3,2.5 or 3.0 mil. depending upon the end use requirements. The outer twolayers of the film are the same and a blend of EVA, LLDPE, and slip. The80% EVA was Exxon LD 712.06, the 9.65% EVA Exxon LD 318.92, the 10%LLDPE Dow 2267A-1 and the 0.35% slip Reed Spectrum 1080823 U slip. Thecore layer was 0.20 mil which was positioned between the two outerlayers and the two inner layers was vinylidene chloride-methyl acrylatecopolymer blended with the appropriate plasticizers, stabilizers andlubricants. The one inner layer positioned next to the core layer was100% Exxon EVA LD 712.06. The inner most layer (sealant layer) was 90%Dow LLDPE 2247A-1 and 10% Equistar LDPE NA 204-000. The thus coextrudedfilm was heated to orientation temperature via a hot water bath (98° C.)and biaxially oriented at a stretch ratio of 3.8×2.7/1. Afterorientation, the film was treated with 4.6 megarads of electron beamirradiation and fabricated into bags for the use in packaging variouscuts of fresh and processed meat products. The bags were heat sealed oncommercial 8300 and 8600 rotary evacuator-sealer equipment availablefrom the Cryovac division of W. R. Grace and Company.

Example 26

[0105] A five layer film was coextruded at a total caliper of 2.25 mil.The first layer of the film was a blend of ethylene vinyl acetatecopolymer, linear low density polyethylene, a second ethylene vinylacetate and slip additive. The 80.0% ethylene vinyl acetate copolymerwas Exxon LD712.06, the 10.0% linear low density polyethylene was Dow2267A-1, the 9.65% second ethylene vinyl acetate copolymer was ExxonLD318.92 and the 0.35% slip additive was Reed Spectrum 1080823. Thesecond layer was ethylene vinyl acetate copolymer. The 100.00% ethylenevinyl acetate copolymer was Exxon LD712-06. The third layer wasvinylidene chloride methyl acrylate copolymer. The 100.00% vinylidenechloride methyl acrylate copolymer was Dow XU32019.19. The fourth layerwas a blend of ethylene vinyl acetate copolymer, linear low densitypolyethylene, a second ethylene vinyl acetate, slip additive and an antiblock additive. The 77.60% ethylene vinyl acetate copolymer was ExxonLD712-06, the 9.70% linear low density polyethylene was Dow 2267A-1, the9.36% second ethylene vinyl acetate copolymer was Exxon LD 318.92, the0.34% slip additive was Reed Spectrum 1080823, the anti block additivewas 1.00% of Ampacet 10579 and 2% processing aids; the fifth layer was ablend of linear low density polyethylene and low density polyethylene.The 90.0% of linear low density polyethylene was Dow 2247A-1 and the10.0% of low density polyethylene was Millennium NA204-00. The thuscoextruded film was heated to orientation temperature via a hot waterbath (98° C.) and biaxially oriented at a stretch ratio of 3.8×2.7/1.After orientation, the film was treated with 4.6 megarads of electronbeam irradiation and fabricated into bags for the use in packagingvarious cuts of fresh and processed meat products. The bags were heatsealed on commercial 8300 and 8600 rotary evacuator-sealer equipmentavailable from the Cryovac division of W. R. Grace and Company.

We claim:
 1. A multiple layer polymer film, comprising: a first layer,the composition of said first layer comprising a blend of an ethylenevinyl acetate copolymer; linear low density polyethylene; a secondethylene vinyl acetate copolymer and slip additive; a second layer, thecomposition of said second layer comprising ethylene vinyl acetatecopolymer and wherein each first and second layer having two surfaces; athird layer, the composition of said third layer comprising vinylidenechloride methyl acrylate copolymer and wherein said third layer isdisposed between said first and second layer; a fourth layer, thecomposition of said fourth layer being the same as said first layerwherein said fourth layer is adhered to said first layer on the surfaceopposite said third layer; and a fifth layer, the composition of saidfifth layer comprising a blend of linear low density polyethylene andlow density polyethylene wherein said fifth layer is adhered to saidsecond layer on the surface opposite said third layer; and wherein anantiblock additive and a slip additive may optionally and independentlybe present in layers 1, 2, 4 and 5 and wherein said antiblock additivemay be a blend of two or more antiblock additives and wherein both ofsaid slip additive and said antiblock additives are present at about0.1%-10%, based on the total weight of the layer.
 2. A multiple layerpolymer film, comprising: a first layer, the composition of said firstlayer comprising a blend of an ethylene vinyl acetate copolymer; linearlow density polyethylene; a second ethylene vinyl acetate copolymer andslip additive; a second layer, the composition of said second layercomprising ethylene vinyl acetate copolymer and wherein each first andsecond layer having two surfaces; a third layer, the composition of saidthird layer comprising vinylidene chloride methyl acrylate copolymer andwherein said third layer is disposed between said first and secondlayer; a fourth layer, the composition of said fourth layer being thesame as said first layer wherein said fourth layer is adhered to saidfirst layer on the surface opposite said third layer; and wherein saidfourth layer further comprises an antiblock additive wherein saidantiblock additive may be a blend of two or more antiblock additives andwherein both of said slip additive and said antiblock additives arepresent at about 0.1%-10%, based on the total weight of the layer; and afifth layer, the composition of said fifth layer comprising a blend oflinear low density polyethylene and low density polyethylene whereinsaid fifth layer is adhered to said second layer on the surface oppositesaid third layer.
 3. The multiple layer polymeric film according toclaim 1 wherein the composition of said first layer is a blend of 80% byweight of ethylene vinyl acetate copolymer, 10% by weight of linear lowdensity polyethylene, 9.65% of ethylene vinyl acetate copolymer and0.35% of slip additive.
 4. The multiple layer polymeric film accordingto claim 1 wherein the composition of said second layer is 100% byweight of ethylene vinyl acetate copolymer.
 5. The multiple layerpolymeric film according to claim 1 wherein the composition of saidthird layer is 98.1% by weight of vinylidene chloride methyl acrylatecopolymer and 1.9% by weight of additives.
 6. The multiple layerpolymeric film according to claim 2 wherein the ethylene vinyl acetatecopolymer which comprises 80% by weight of said first layer has a vinylacetate content of 10%, a melt index of 0.35 g/10 min and a density of0.931 g/cm³.
 7. The multiple layer polymeric film according to claim 2wherein the ethylene vinyl acetate copolymer which comprises 9.65% byweight of said first layer has a vinyl acetate content of 9.0%, a meltindex of 2.0 g/10 min and a density of 0.930 g/cm³.
 8. The multiplelayer polymeric film according to claim 3 wherein the composition ofsaid second layer is 100% by weight of ethylene vinyl acetate copolymerand said ethylene vinyl acetate copolymer has a vinyl acetate content of10%, a melt index of 0.35 g/10 min and a density of 0.931 g/cm³.
 9. Themultiple layer polymeric film according to claim 1 wherein thecomposition of said fourth layer is a blend of 77.60% by weight ofethylene vinyl acetate copolymer; 9.70% by weight of linear low densitypolyethylene; 9.36% by weight of a second ethylene vinyl acetatecopolymer; and 0.35% by weight of slip additive, 1% by weight ofantiblock additive and 2% by weight of processing aids.
 10. The multiplelayer polymeric film according to claim 1 wherein the composition ofsaid fifth layer is a blend of 90% by weight of linear low densitypolyethylene and 10% by weight of low density polyethylene.
 11. Themultiple layer polymeric film structure according to claim 1 wherein theantiblock additive is Ampacet
 10579. 12. The multiple layer polymericfilm structure according to claim 1 wherein the antiblock additive isAmpacet
 7012124. 13. The multiple layer polymeric film structureaccording to claim 1 wherein the antiblock additive is a blend ofAmpacet 7012124 and Ampacet
 10579. 14. The multiple layer polymeric filmstructure according to claim 1 wherein the antiblock additive blend ispresent up to 3% of the total weight of the fourth layer.
 15. Amolecularly oriented multiple layer polymeric film comprising: a firstlayer, the composition of said first layer comprising a blend of anethylene vinyl acetate copolymer; linear low density polyethylene; asecond ethylene vinyl acetate copolymer; and slip additive; a secondlayer, the composition of said second layer comprising ethylene vinylacetate copolymer and wherein each first and second layer having twosurfaces; a third layer, the composition of said third layer comprisingvinylidene chloride methyl acrylate copolymer and wherein said thirdlayer is disposed between said first and second layer; a fourth layer,the composition of said fourth layer being the same as said first layerwherein said fourth layer is adhered to said first layer on the surfaceopposite said third layer; and wherein said fourth layer furthercomprises an antiblock agent wherein said antiblock agent may be a blendof two or more antiblock agents and wherein both of said slip additiveand said antiblock agents are present at about 0.1%-10%, based on thetotal weight of the layer; and a fifth layer, the composition of saidfifth layer comprising a blend of linear low density polyethylene andlow density polyethylene wherein said fifth layer is adhered to saidsecond layer on the surface opposite said third layer.
 16. Themolecularly oriented multiple layer film according to claim 15 whereinthe composition of said first layer is a blend of 80% by weight ofethylene vinyl acetate copolymer; 10% by weight of linear low densitypolyethylene; 9.65% by weight of a second ethylene vinyl acetatecopolymer; and 0.35% by weight of slip additive.
 17. The molecularlyoriented multiple layer film according to claim 15 wherein thecomposition of said second layer is 100% by weight of ethylene vinylacetate copolymer.
 18. The molecularly oriented multiple layer filmaccording to claim 15 wherein the composition of said third layer is98.1% by weight of vinylidene chloride methyl acrylate copolymer and1.9% by weight of additive.
 19. The molecularly oriented multiple layerfilm according to claim 15 wherein the ethylene vinyl acetate copolymerwhich comprises 80% by weight of said first layer has a vinyl acetatecontent of 10%, a melt index of 0.35 and a density of 0.931 g/cm³. 20.The molecularly oriented multiple layer film according to claim 15wherein the ethylene vinyl acetate copolymer which comprises 9.65% byweight of said first layer has a vinyl acetate content of 9.0%, a meltindex of 2.0 and a density of 0.930 g/cm³.
 21. The molecularly orientedmultiple layer film according to claim 15 wherein the composition ofsaid second layer is 100% by weight of ethylene vinyl acetate copolymerand said ethylene vinyl acetate has a vinyl acetate content of 10%, amelt index of 0.35 g/10 min and a density of 0.931 g/cm³.
 22. Themolecularly oriented multiple layer film according to claim 15 whereinthe composition of said fourth layer is a blend of 77.6% by weight ofethylene vinyl acetate copolymer; 9.70% by weight of linear low densitypolyethylene; 9.36% by weight of a second ethylene vinyl acetatecopolymer; and 0.35% by weight of slip additive, 1% by weight of anantiblock agent and 2% by weight of processing aids.
 23. The molecularlyoriented multiple layer film according to claim 10 wherein thecomposition of said fifth layer is a blend of 90% by weight of linearlow density polyethylene and 10% by weight of low density polyethylene.24. A bag made from the film of claim 2 .
 25. A bag made from the filmof claim 15 .
 26. A multiple layer polymeric film comprising: a firstlayer, the composition of said first layer comprising a blend of 80% byweight ethylene vinyl acetate copolymer, 10% by weight of linear lowdensity polyethylene; 9.65% by weight of a second ethylene vinyl acetatecopolymer; and 0.35% by weight of slip additive. a second layer, thecomposition of said second layer comprising 100% ethylene vinyl acetatecopolymer and wherein each first and second layer having two surfaces; athird layer, the composition of said third layer comprising 100%vinylidene chloride methyl acrylate copolymer and wherein said thirdlayer is disposed between said first and second layer; a fourth layer,the composition of said fourth layer being the same as said first layerwherein said fourth layer is adhered to said first layer on the surfaceopposite said third layer; and wherein said fourth layer furthercomprises an antiblock additive wherein said antiblock additive may be ablend of two or more antiblock additives and wherein both of said slipadditive and said antiblock additives are present at about 0.1%-10%,based on the total weight of the layer; and a fifth layer, thecomposition of said fifth layer comprising a blend of 90% linear lowdensity polyethylene and 10% by weight of low density polyethylenewherein said fifth layer is adhered to said second layer on the surfaceopposite said third layer.
 27. A multiple layer polymeric film accordingto claim 26 wherein the composition of said fourth layer comprises77.60% by weight of ethylene vinyl acetate copolymer, 9.7% by weight oflinear low density polyethylene, 9.36% by weight of a second ethylenevinyl acetate copolymer, 0.34% by weight of slip additive, 1.0% byweight of an antiblock additive and 2% by weight of processing aids. 28.A multiple layer polymeric film according to claim 26 which can bemolecularly oriented.
 29. A bag made from the film of claim 27 .